DE19711825A1 - Substituted 2,4-diamino-1,3,5-triazines - Google Patents

Abstract

The invention relates to novel substituted 2,4-diamino-1,3,5-triazines of formula (I), wherein R<1> stands for (respectively unsubstituted ) phenyl or naphthyl, R<2> stands for alkyl, R<3> represents hydrogen, halogen or respectively optionally substituted alkyl, alkoxy, alkythio, alkyl sulfinyl or alkyl sulfonyl, R<4> represents hydrogen, halogen or optionally substituted alkyl, R<5> is hydrogen, halogen or optionally substituted alkyl, R<6> is hydrogen or a respectively optionally substituted alkyl carbonyl or alkyl sulfonyl, (wherein the compound 2-amino-4-(1-phenyl-ethylamino)-6-trifluoromethyl-1,3,5,-triazine is however excluded). The invention also relates to methods for the production of novel compounds and the use thereof as herbicides.

Description

The invention relates to new substituted 2,4-diamino-1,3,5-triazines, processes for their manufacture and their use as herbicides.

A number of substituted 2,4-diamino-triazines, such as. B. the connection 2- Amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine, is already from the (Patent) literature known (cf. US 3816419, cf. also US 3932167, EP 191496, EP 273328, EP 411153 / WO 90/09378). So far, however, these connections have none attained special importance.

The new substituted 2,4-diamino-1,3,5-triazines of the general formula (I) have now been found

in which
R ^{1 represents} (in each case unsubstituted) phenyl or naphthyl,
R ^{2 represents} alkyl,
R ^{3 represents} hydrogen, halogen or optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl,
R ^{4 represents} hydrogen, halogen or optionally substituted alkyl,
R ^{5 represents} hydrogen, halogen or optionally substituted alkyl, and
R ^{6 represents} hydrogen or represents optionally substituted alkyl, alkyl carbonyl or alkylsulfonyl,
however, the known compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine (cf. US 3816419) is excluded by disclaimer.

The new substituted 2,4-diamino-1,3,5-triazines of the general formula (I) are obtained if

• (a) substituted biguanides of the general formula (II)
  in which
  R ¹ , R ² and R ^{6 have} the meaning given above, and / or acid adducts of compounds of the general formula (II)
  with alkoxycarbonyl compounds of the general formula (III)
  in which
  R ³ , R ⁴ and R ^{5 have} the meaning given above and
  R represents alkyl,
  if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
  or if you
• (b) for the preparation of compounds of the formula (I) in which R ^{6 is} different from hydrogen,
  2,4-diamino-1,3,5-triazines of the general formula (Ia)
  in which
  R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meaning given above,
  with alkylating, acylating or sulfonylating agents of the general formula (IV)
  XR ⁶ (IV)
  in which
  R ⁶ has the meaning given above with the exception of hydrogen and
  X represents halogen, alkoxy, acyloxy or alkoxysulfonyloxy,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and optionally on the compounds of the general formula (I) obtained according to the processes described under (a) or (b), as part of the above substituent definition, further conversions are carried out by customary methods.

The new substituted 2,4-diamino-1,3,5-triazines of the general formula (I) are characterized by strong and selective herbicidal activity.

Surprisingly, the 2,4-diamino-1,3,5-triazines of the invention show all general formula (I) with good tolerance to crops, such as e.g. B. barley and cotton, much stronger herbicidal activity than the previous Known compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine.

The compounds of general formula (I) according to the invention contain mind least an asymmetrically substituted carbon atom and can therefore be ver different enantiomers (R- and S-configured forms) and diastereomers Shapes are available. The invention relates to both the different possible ones individual enantiomeric or stereoisomeric forms of the compounds of the general Formula (I) as well as the mixtures of these isomeric compounds.

In the definitions, the hydrocarbon chains, such as alkyl, are also linked with heteroatoms, such as in alkoxy or alkylthio - in each case straight-chain or branched.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably Fluorine, chlorine or bromine, especially for fluorine or chlorine.

The invention preferably relates to compounds of the formula (I) in which
R ^{1 represents} (in each case unsubstituted) phenyl or naphthyl,
R ^{2 represents} alkyl having 1 to 6 carbon atoms,
R ^{3 represents} hydrogen, halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each of which has 1 to 6 carbon atoms and is optionally substituted by halogen or C ₁ -C ₄ -alkoxy,
R ^{4 represents} hydrogen, halogen or alkyl optionally substituted by halogen,
R ^{5 represents} hydrogen - halogen or alkyl optionally substituted by halogen, and
R ^{6 represents} hydrogen or alkyl, alkylcarbonyl or alkylsulfonyl which is optionally substituted by halogen or C ₁ -C ₄ -alkoxy,
the known compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine (cf. US 3816419) being excluded by disclaimer.

The invention relates in particular to compounds of the formula (I) in which
R ^{1 represents} (in each case unsubstituted) phenyl or naphthyl,
R ^{2 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R ^{3 represents} hydrogen, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl , Ethylsulfinyl, methylsulfonyl or ethylsulfonyl,
R ^{4 stands} for hydrogen, for fluorine, chlorine or bromine, or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine,
R ^{5 represents} hydrogen, fluorine, chlorine or bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine, and
R ^{6 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n- or i-, each optionally substituted by fluorine, chlorine, methoxy or ethoxy Butyroyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl,
the known compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine (cf. US 3816419) being excluded by disclaimer.

The general or priority ranges listed above nitions apply both to the end products of formula (I) and accordingly to the starting or intermediate products required for the production. This Residual definitions can be between themselves, that is, between the specified ones areas can be combined as required.

If, for example, 1- (1-phenyl-propyl) biguanide and methyl trifluoroacetate are used as starting materials, the course of the reaction in process (a) according to the invention can be outlined using the following formula:

If, for example, 2-amino-4- (2,2,2-trifluoro-1-methyl-ethyl) -6- (1-phenyl-ethylamino) -1,3,5-triazine and acetyl chloride are used as starting materials, the The course of the reaction in process (b) according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the substituted biguanides to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I). In the formula (II), R ¹ , R ² and R ^{6 are} preferred or, in particular, those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention or as particularly preferred for R ¹ , R ² and R ^{6 were} given.

Suitable acid adducts of compounds of the formula (II) are their additions products with protonic acids, such as B. with hydrogen chloride (hydrogen chloride), Hydrogen bromide (hydrogen bromide), sulfuric acid, methanesulfonic acid, benzene sulfonic acid and p-toluenesulfonic acid.

The starting materials of the general formula (II) are known and / or can be according to processes known per se (cf. US 3816419; Indian J. Chem. 1 (1963), 218-220; J. Am. Chem. Soc. 81: 3728-3736 (1959).

The substituted biguanides of the general formula (II) are obtained if amines of the general formula (VII)

in which
R ¹ and R ^{2 have} the meaning given above,
- And / or acid adducts of compounds of general formula (V), such as. B. the hydrochloride -
with cyanoguanidines of the general formula (VI)

in which
R ^{6 has} the meaning given above,
optionally in the presence of a reaction auxiliary, such as. B. hydrogen chloride, and optionally in the presence of a diluent, such as. B. n-decane, toluene or 1,2-dichlorobenzene, at temperatures between 100 ° C and 200 ° C (see. The preparation examples).

Formula (III) provides a general definition of the alkoxycarbonyl compounds to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I). In the formula (III), R ³ , R ⁴ and R ⁵ preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ³ , R ⁴ and R ^{5 were} given; R preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.

The starting materials of the formula (III) are known synthetic chemicals.

Formula (Ia) provides a general definition of the 2,4-diamino-1,3,5-triazines to be used as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I). In the formula (Ia), R ¹ , R ² , R ³ , R ⁴ and R ⁵ preferably or in particular have those meanings which are preferred or particularly in connection with the description of the compounds of the formula (I) according to the invention were preferably given for R ¹ , R ² , R ³ , R ⁴ and R ⁵ .

The starting materials of the general formula (Ia) are also new compounds Subject of the present application; they can be prepared according to method (a) will.

Formula (IV) provides a general definition of the alkylating, acylating or sulfonylating agents which are further to be used as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I). In formula (IV), R ⁶ preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ⁶ , with the exception of hydrogen-X preferably represents fluorine, chlorine, bromine, iodine, methoxy, ethoxy, acetyloxy, propionyloxy, methoxysulfonyloxy or ethoxy sulfonyloxy.

The starting materials of the general formula (VI) are known synthetic chemicals.

The processes according to the invention for the preparation of the compounds of the formula (I) are optionally carried out using a reaction auxiliary. The usual reaction auxiliaries for processes (a) and (b) organic or organic bases or acid acceptors. For this ge  preferably hear alkali metal or alkaline earth metal acetates, amides, carbonates, -hydrogen carbonates, -hydrides, -hydroxides or -alkanolates, such as Sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, Sodium, potassium or calcium hydroxide, sodium or potassium methoxide, -ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; continue too basic organic nitrogen compounds, such as trimethylamine, tri ethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclo hexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-Di methyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-di methyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine '4-di methylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU).

As a diluent for carrying out processes (a) and (b) inert organic solvents may be used. For this include in particular aliphatic, alicyclic or aromatic, optionally halo Hydrogenated hydrocarbons such as gasoline, benzene, toluene, xylene, chlorine benzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, Carbon tetrachloride, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro furan or ethylene glycol dimethyl or diethyl ether; Ketones such as methyl isopropyl ketone or methyl isobutyl ketone; Nitriles, such as acetonitrile, propionitrile or butyro nitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl form anilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters like vinegar acid methyl ester or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Alko get, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be carried out when carrying out the inventive Processes (a) and (b) can be varied over a wide range. In general  one works at temperatures between 0 ° C and 180 ° C, preferably between 10 ° C and 150 ° C.

Processes (a) and (b) according to the invention are generally described under Normal pressure carried out. However, it is also possible to use the inventive Processes under increased or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The Reaction is generally carried out in a suitable diluent were carried out a reaction auxiliary and the reaction mixture is in space agitated several hours at the required temperature. The on work is carried out according to customary methods (cf. the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, kraut tabs killers and especially used as a weed killer. Weeds in the broadest sense are understood to mean all plants that are found in places grow where they are undesirable. Whether the substances according to the invention as total or Selective herbicides act essentially depends on the amount used.

The active compounds according to the invention can, for. B. used in the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Ahthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduanum, Carduus, Sol , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicot cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecums, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to these Limited genres, but extends in the same way to others Plants.

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the connections to weed beds fighting in permanent crops, e.g. B. forest, ornamental wood, fruit, wine, citrus, nut, Banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hops plants, on ornamental and sports turf and pastures and for selective weeds fighting in annual crops.

The compounds of formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledons and dicotyledon cultures both pre-emergence and post-emergence.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.  

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, if necessary using surface-active agents, that is Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformainide and dimethyl sulfoxide, and water.

As solid carriers come into question: B. ammonium salts and natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silicic acid, aluminum oxide and silicates, come as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules made of organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam Generating funds are possible: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants come into question: z. B. lignin sulfite and Methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho  lipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient - preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides are suitable for the mixtures, for example Acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Asulam, Atrazine, Azimsulfuron, Ben azoline, benfuresate, bensulfuron (methyl), bentazone, benzofenap, benzoylprop ( ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, Butylates, cafenstroles, carbetamides, chloromethoxyfen, chloramben, chloridazon, Chlorimuron (-ethyl), chloronitrofen, chlorosulfuron, chlorotoluron, cinmethylin, Cinosulfuron, Clethodim, Clodinafop (-propargyl), Clomazone, Clopyralid, Clo pyrasulfuron, chlorosulam (methyl), cumyluron, cyanazines, cycloates, cyclo sulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedi pham, dialallate, dicamba, diclofop (methyl), difenzoquat, diflufenican, di mefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, di nitramine, diphenamide, diquat, dithiopyr, diuron, dymron, EPTC, Esprocarb, Ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, etobenzanide, Fenoxaprop (-ethyl), Flamprop (-isopropyl), Flamprop (-isopropyl-L), Flamprop (- methyl), flazasulfuron, fluazifop (-butyl), flumetsulam, flumiclorac (-pentyl),  Flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen (- ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, Flurtamone, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropyl ammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinones, imazamethabenz (- methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazo sulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Metamitron, Metazachlor, Methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Napro anilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, Oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquiza fop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (-ethyl), Pyrazoxyfen, Pyributicarb, Pyridate, Pyrithiobac (-sodium), Quinchlorac, Quin merac, quizalofop (-ethyl), quizalofop (-p-tefuryl), rimsulfuron, sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, Thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifluralin and triflusulfuron.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plant nutrients fabrics and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used will. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.  

The active compounds according to the invention can be used both before and after emergence of the plants are applied. They can also be planted in the soil before sowing be working.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 1 g and 10 kg of active ingredient per hectare of soil area, preferably between 5 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention are based on following examples.

Manufacturing examples example 1

Procedure (a)

A solution of 3.5 g (65 mmol) of sodium methylate in 15 ml of methanol is added dropwise as with stirring at 20 ° C to a mixture of 15.5 g (60 mmol) of 1- (1-phenyl propyl) biguanide (racemic), 8.0 g (60 mmol) of ethyl 2-fluoropropanoate and 100 ml of methanol are added and the reaction mixture is then a further 15 hours Room temperature (about 20 ° C) stirred. Then it is ge with methylene chloride and water shakes, the organic phase separated, washed with 1N sodium hydroxide solution with Dried sodium sulfate and filtered. The filtrate becomes in a water jet vacuum The solvent is carefully distilled off.

13 g (78% of theory) of 2-amino-4- (1-fluoro-ethyl) -6- (1-phenyl-propyl) are obtained amino) -1,3,5-triazine (racemate) as an amorphous residue.

Example 2

Method (b)

A mixture of 10 g (36 mmol) of 2-amino-4- (1-fluoro-ethyl) -6- (1-phenyl-propyl amino) -1,3,5-triazine (racemic) and 70 ml acetic anhydride is 2 hours at 130 ° C. stirred and after cooling to room temperature (about 20 ° C) with 150 ml of water and 150 ml of methylene chloride are stirred. The organic phase is then separated off with Dried sodium sulfate and filtered. The filtrate is immersed in a water jet vacuum concentrated, the residue digested with a little ethanol and the crystalline product isolated by suction.

2.2 g (19% of theory) of 2-acetylamino-4- (1-fluoro-ethyl) -6- (1-phenyl) are obtained propylamino) -1,3,5-triazine (racemate) melting point 118 ° C.

Analogously to preparation examples 1 and 2 and in accordance with the general description of the preparation processes according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in table 1 below.

Examples of the compounds of the formula (I)

Examples of the compounds of the formula (I)

Starting materials of formula (II) Example (II-1)

A mixture of 27 g (0.21 mol) 1-phenylethylamine (racemic), 22 ml 33% aqueous hydrochloric acid and about the same amount of toluene is in a water jet vacuum evaporated to dryness. 17 g (0.21 mol) of dicyan to the residue added diamid (cyanoguanidine) and the mixture is then left on for 2 hours 150 ° C heated, whereby a melt is formed.

The crude product thus obtained - 1- (1-phenyl-propyl) biguanide hydrochloride (race mixed) - is used directly for the preparation of compounds of the formula (I).

Analogously to Example (II-1), those in Table 2 below can also be used, for example Compounds of formula (11) listed or their hydrochlorides prepared will.

Examples of the compounds of the formula (II)

Examples of the compounds of the formula (II)

Examples of use

In the following application examples, the known compound (A) is used as a reference substance:

2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine (see US 3816419)  

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours the soil is poured with the active ingredient preparation. You keep the water quantity per unit area expediently constant. The drug concentration in the preparation does not matter, only the application rate of the Active ingredient per unit area.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, the compounds according to Preparation Example 1 show 2, 13, 14, 15, 16, 17 and 18 with good tolerance to culture plants, such as B. cotton, barley and rapeseed, significantly stronger effect against Weeds as the known compound (A).  

Example B Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

With the active ingredient preparation, test plants are sprayed, which have a height of 5 to 15 cm so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 1000 l water / ha the desired amounts of active ingredient are applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, the compounds according to Preparation Example 1 show 2, 13 and 18 with good tolerance to crops, such as. B. Wheat and barley, considerably more effective against weeds than the known one Compound (A).

Claims (8)

1. Substituted 2,4-diamino-1,3,5-triazines of the formula (I),
in which
R ^{1 represents} (in each case unsubstituted) phenyl or naphthyl,
R ^{2 represents} alkyl,
R ^{3 represents} hydrogen, halogen or optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl,
R ^{4 represents} hydrogen, halogen or optionally substituted alkyl,
R ^{5 represents} hydrogen, halogen or optionally substituted alkyl, and
R ^{6 stands} for hydrogen or for optionally substituted alkyl, alkylcarbonyl or alkylsulfonyl,
however, the compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine is excluded. 2. Compounds of formula (I) according to claim 1, characterized in that therein
R ^{1 represents} (in each case unsubstituted) phenyl or naphthyl,
R ^{2 represents} alkyl having 1 to 6 carbon atoms,
R ^{3 represents} hydrogen, halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each of which has 1 to 6 carbon atoms and is optionally substituted by halogen or C ₁ -C ₄ -alkoxy,
R ^{4 represents} hydrogen, halogen or alkyl optionally substituted by halogen,
R ^{5 represents} hydrogen, halogen or alkyl optionally substituted by halogen, and
R ^{6 represents} hydrogen or alkyl, alkylcarbonyl or alkylsulfonyl which is optionally substituted by halogen or C ₁ -C ₄ alkoxy,
the compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine being excluded. 3. Compounds of formula (I) according to claim 1, characterized in that therein
R ^{1 represents} (in each case unsubstituted) phenyl or naphthyl,
R ^{2 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R ^{3 represents} hydrogen, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, Ethylsulfinyl, methylsulfonyl or ethylsulfonyl,
R ^{4 represents} hydrogen, fluorine, chlorine or bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine,
R ^{5 represents} hydrogen, fluorine, chlorine or bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine, and
R ^{6 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n- or i-, each optionally substituted by fluorine, chlorine, methoxy or ethoxy Butyroyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butyl sulfonyl,
the compound 2-amino-4- (1-phenyl-ethylamino) -6-trifluoromethyl-1,3,5-triazine being excluded. 4. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• (a) substituted biguanides of the general formula (II)
  in which
  R ¹ , R ² and R ^{6 have} the meaning given in claim 1,
  • and / or acid adducts of compounds of the general formula (II)
    with alkoxycarbonyl compounds of the general formula (III)
    in which
    R ³ , R ⁴ and R ^{5 have} the meaning given in claim 1 and
    R represents alkyl,
    if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
    or that one
• (b) for the preparation of compounds of the formula (I) in which R ^{6 is} different from hydrogen,
  2,4-diamino-1,3,5-triazines of the general formula (Ia)
  in which
  R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meaning given in claim 1,
  with alkylating, acylating or sulfonylating agents of the general formula (IV)
  XR ⁶ (IV)
  in which
  R ^6, with the exception of hydrogen, has the meaning given in claim 1 and
  X represents halogen, alkoxy, acyloxy or alkoxysulfonyloxy,
  if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
  and optionally on the compounds of the general formula (I) obtained according to the processes mentioned under (a) or (b) in the context of the above definition of substituents, further conversions are carried out by customary methods.

5. Herbicidal agents, characterized by a content of at least one A compound of formula (I) according to claim 1.   6. Use of compounds of general formula (I) according to claim 1 to combat unwanted plant growth. 7. A method of combating weeds, characterized in that to compounds of the general formula (I) according to claim 1 Weeds or their habitat. 8. A process for the preparation of herbicidal compositions, characterized in that that compounds of the general formula (I) according to Claim 1 with Extenders and / or surfactants mixed.